JP2001030436A - Decorative plate and its laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve mechanical characteristics and thermal characteristics of a decorative plate frequently used for surface decorating of a furniture or fittings, interior finishing of a building or the like or particularly scratch resistance and cigarette resistance by uniformly dispersing a silicate complex made of a lubricating laminar silicate and a positive charge organic compound in a thermoplastic resin. SOLUTION: The decorative plate is formed by using a resin composite obtained by uniformly dispersing a silicate complex made of a swelling laminar silicate and a positive charge organic compound in a resin such as a thermoplastic resin, for example, like a polypropylene resin, polyamide resin, polyacetal resin or the like. In this case, as the resin composite, a complex containing 0.5 to 40 pts.wt. of a silicate complex per 100 pts.wt. of the thermoplastic resin is preferred. The swelling laminate silicate to be used is a laminar crystal and belongs to phyllosilicates in a mineralogy. As the laminate silicate, a smectite, mica or the like is used. As the positive charge organic compound, a triazine compound such as a melamine compound, cyanuric acid compound or the like is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is excellent in mechanical properties, dimensional stability, scratch resistance, cigarette resistance and sliding abrasion resistance, and is suitable for furniture and fittings, cosmetics for interiors of buildings and interiors of vehicles. And a laminate thereof.

[0002]

2. Description of the Related Art Engineering plastics such as polyamide resins have excellent heat resistance, oil resistance, and mechanical strength, and are used in a wide range of fields, including automobile parts, electric and electronic parts, home appliances, industrial equipment, and daily necessities. ing. Recently, it is also used for building materials such as office furniture and sashes and handles, so that its design and surface properties are required to be improved.In particular, improvements in scratch resistance, cigarette resistance and sliding abrasion resistance are required. ing. Further, polyolefins which have been studied as substitutes for vinyl chloride resin due to environmental problems are lacking the above properties, and improvement has been desired. As a method for improving this, a method of blending a filler has been proposed.

[0003]

However, in the method of blending the filler, there is a problem that the improvement effect cannot be exhibited unless a considerable amount is used, and that the surface condition is deteriorated.

[0004]

Means for Solving the Problems The present inventors have carried out sincere studies in order to solve the problems of the prior art as described above, and as a result, have accomplished the present invention. That is, the present invention provides a decorative board comprising a resin composite obtained by uniformly dispersing a silicate composite comprising a swellable layered silicate and a positively charged organic compound in a thermoplastic resin.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The thermoplastic resin in the present invention is not particularly limited in kind, and examples thereof include a polypropylene resin, a polyamide resin, a polyacetal resin, a polycarbonate resin, and a polyester resin. All of these resins are industrialized and consumed in large quantities, and include various publications (for example, “Practical Plastics Glossary Dictionary Third Edition” (published by Plastic Age Co., Ltd.) and “New Edition Polymer Dictionary”. (Published by Asakura Shoten), "12695 Chemical Products" (published by Chemical Daily), etc.). Among these, a polyamide resin is preferable.

The swellable phyllosilicate used in the present invention is rich in changes such as the chemical composition and crystal structure, and there is no established classification and nomenclature. The feature of the layered silicate here is a layered crystal, which belongs to phyllosilicate on mineralogy,
Among them, a 2: 1 type phyllosilicate composed of two tetrahedral layers and one octahedral layer, and a 1: 1 type phyllosilicate composed of one tetrahedral layer and one octahedral layer are exemplified. . Typical minerals of 2: 1 type phyllosilicate include smectite, vermiculite, mica and chlorite, and 1: 1 type phyllosilicate includes kaolin, serpentine and the like. The smectite group includes saponite, hectorite, sauconite, montmorillonite,
There are beiderite, nontronite, stephensite, etc., the vermiculite group includes trioctahedral vermiculite, dioctahedral vermiculite, etc. Compositions such as chlorite, margarite, teniolite, and tetrasilicic mica are exemplified. These phyllosilicates may be produced naturally or synthesized by a hydrothermal method, a melting method, a solid phase method, or the like.

The type of the positively charged organic compound used in the present invention is not particularly limited, but preferred examples thereof include triazine compounds such as melamine compounds, cyanuric acid compounds and melamine cyanurate compounds, primary amines and secondary amines. , Tertiary amines and their chlorides, quaternary ammonium salts, amine compounds, amino acid derivatives, nitrogen-containing heterocyclic compounds, and phosphonium salts.
Specifically, melamine compounds such as melamine hydrochloride and N-melamine hydrochloride; typified by octylamine, laurylamine, tetradecylamine, hexadecylamine, stearylamine, oleylamine, acrylamine, benzylamine, aniline, etc. Primary amines: dilaurylamine, ditetradecylamine, dihexadecylamine,
Secondary amines represented by distearylamine, N-methylaniline, etc .: dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylmyristylamine, dimethylpalmitylamine, dimethylstearylamine, dilaurylmonomethylamine, tributylamine, Tertiary amines represented by trioctylamine, N, N-dimethylaniline, etc .; tetrabutylammonium ion, tetrahexylammonium ion, dihexyldimethylammonium ion, dioctyldimethylammonium ion, hexatrimethylammonium ion, octatrimethylammonium ion, dodecyl Trimethylammonium ion, hexadecyltrimethylammonium ion, stearyltrimethylammonium ion, doco Nyl trimethyl ammonium ion, cetyl trimethyl ammonium ion, cetyl triethyl ammonium ion, hexadecyl ammonium ion, tetradecyl dimethyl benzyl ammonium ion, stearyl dimethyl benzyl ammonium ion, dioleyl dimethyl ammonium ion, N-methyldiethanol lauryl ammonium ion, dipropanol monomethyl Lauryl ammonium ion, dimethyl monoethanol lauryl ammonium ion, polyoxyethylene dodecyl monomethyl ammonium ion,
And quaternary ammoniums such as alkylaminopropylamine quaternaries. In addition, Leucine, Sistine,
Phenylalanine, tyrosine, aspartic acid, glutamic acid, lysine, 6-aminohexylcarboxylic acid, 12
-Aminolaurylcarboxylic acid, N, N-dimethyl-6-
Aminohexyl carboxylic acid, Nn-dodecyl-N, N
-Dimethyl 10-aminodecylcarboxylic acid, dimethyl-
Amino acid derivatives such as N-12 aminolauryl carboxylic acid; pyridine, pyrimidine, pyrrole, imidazole,
Examples include nitrogen-containing heterocyclic compounds such as proline, γ-lactam, histidine, tryptophan, aniline, and quinuclidine.

In the present invention, the amount of the positively charged organic compound is determined based on the cation exchange capacity (hereinafter referred to as “CE”) of the layered silicate.
C ". ) Is preferably 0.3 to 3 equivalents, particularly preferably 0.1 to 3 equivalents.
5 to 2.0 equivalents are most preferred. In addition, C of layered silicate
EC differs depending on the type, locality, and composition of the layered silicate, and therefore needs to be measured in advance. Also CE
C can be obtained by a method such as a column permeation method (refer to “Clay Handbook”, pp. 567-577, published by Kikudo) or a method for measuring the amount of adsorbed methylene blue (Standard Test Method of Japan Bentonite Industry Association, JBAS-107-91). Measured.

The silicate composite of the present invention can be obtained by subjecting the positively charged organic compound to an ion exchange reaction with the swellable layered silicate, but the production method is not particularly limited. Specifically, after the powder of the swellable phyllosilicate is sufficiently solvated with water, alcohol, or the like, the above positively charged organic compound is added, and the mixture is stirred and replaced with a metal cation present between the layers of the swellable phyllosilicate. Let it. Thereafter, the formed precipitate is filtered and dried to obtain a silicate complex. At that time, the unsubstituted positively charged organic compound may be removed by washing.

[0010] The amount of the silicate composite added is as follows.
The amount is preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight, per 100 parts by weight. If the added amount of the silicate composite is less than 0.5 part by weight, the effect of improving scratch resistance and cigarette resistance is poor. On the other hand, if it exceeds 40 parts by weight, there is a possibility that the sliding wear property and the formability are reduced.

The resin composite of the present invention can be obtained by kneading a thermoplastic resin and the above silicate composite by a method usually employed in the field of synthetic resins. For example, powder, flakes, pellets and other arbitrary forms of thermoplastic resin and silicate composite tumbler, super mixer,
After sufficiently mixing with a ribbon mixer or the like, a method of melt-kneading at a temperature equal to or higher than the melting point with a melt-kneading apparatus such as a Banbury mixer, a continuous mixer with a rotor, or a twin-screw extruder may be used. By such a kneading operation, the silicate composite can be uniformly dispersed in the thermoplastic resin.

After the above-mentioned kneading operation, the decorative board of the present invention is formed by a forming method such as extrusion molding, injection molding, compression molding and blow molding. The obtained decorative board can be suitably used for surface decoration of furniture and fittings, interior of buildings, interior of vehicles and the like. Further, the decorative board of the present invention may be used by being laminated with another base material, for example, paper, synthetic resin, wood board, plywood, metal, glass or the like. The shape of the base material is not particularly limited, and may be a shape such as a honeycomb, a corrugated shape, an unevenness, a perforated plate, a net, a foam, a cotton swab, or a powder. As a lamination method, a conventionally known method can be adopted,
For example, a dry lamination method using a urethane-based adhesive or the like can be given.

Furthermore, the decorative board of the present invention can contain various additives commonly used in the art, depending on the intended use. For example, various colorants, lubricants, release agents, surfactants, heterogeneous polymers, organic polymer improvers, antioxidants, light resistance agents, antistatic agents, electric insulation improvers, fungicides, inorganic, organic In addition, a fibrous, powdery or plate-like filler such as metal, and other additives may be blended within a range that does not impair the effects of the present invention and the performance of the composite material. The blending of these additives and the like may be added at any arbitrary stage,
It can be added and mixed just before obtaining the final molded article.

[0014]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. In addition, the measuring method of each physical property is shown below. (1) Tensile strength and tensile elongation According to ASTM D638, temperature 23 ° C, tensile speed 5
The measurement was performed under the condition of 0 mm / min. (2) Scratch resistance The surface of the sheet was scratched with an HB pencil, and the degree of remaining scratches was visually evaluated in the following three grades. ○ ・ ・ ・ ・ No damage △ ・ ・ ・ ・ Slightly damaged × ・ ・ ・ ・ Clearly scratched (3) Cigarette resistance Place a lit cigarette horizontally on the sheet, and after 30 seconds, scorch and deform It was visually observed and evaluated in the following four stages. ◎ ··· Burns but leaves no trace when wiped ○ · · · Burns and leaves traces even when wiped △ · · · Burns and deforms slightly × · · · Burns and holes (4) Slip resistance Abrasion In accordance with JIS K7218, cylindrical test pieces (inner diameter 2
0.0mm, outer diameter 25.6mm, height 15.0mm) was subjected to a thrust wear test with steel (S45C) under the conditions of a surface contact pressure of 10kg / cm2 and a sliding speed of 30cm / sec.
The kinetic friction coefficient, the specific wear amount and the critical PV value were measured.

As the thermoplastic resin, polyamide 6 having a relative viscosity of 4.5 (hereinafter referred to as "PA1") and polyamide 66 having a relative viscosity of 3.5 (hereinafter referred to as "PA2") were used.

Production Example of Silicate Complex A synthetic mica ("ME-100", manufactured by Corp Chemical Co., cation exchange capacity (CEC) = 107 meq / 100 g) was used as layered silicate in distilled water (4 L) at 60 ° C. 200
g. After dissolving 1 equivalent of melamine hydrochloride with respect to CEC in distilled water at a temperature of 60 ° C., the solution was added to the layered silicate dispersion and stirred at 60 ° C. for 2 hours. The resulting precipitate was washed, filtered, dried, and then pulverized to obtain a silicate complex (hereinafter, referred to as “SC1”). Obtained S
The distance between the bottom surfaces of C1 was 1.3 nm, and the melamine hydrochloride content was 11% by weight. The distance between the bottom surfaces was determined by using an X-ray diffractometer (Rigaku Denki Co., RINT2000, CuKα-40k).
V, 20 mA). In addition, the melamine hydrochloride content was measured using a differential thermal / thermogravimetric simultaneous measurement device (manufactured by Seiko Instruments Inc.) (hereinafter referred to as “TG-DTA”).

As a layered silicate, natural montmorillonite ("Kunipia-F" manufactured by Kunimine Industries, CEC = 1)
Silicate composite (hereinafter, referred to as “SC2”) was obtained in the same manner as described above except that the amount of the silicate composite (00meq / 100g) was used. SC
2, the bottom distance was 1.4 nm, and the melamine hydrochloride content was 1
It was 1% by weight.

Examples 1 and 2, Comparative Examples 1 to 5 Blends were blended in the types and amounts shown in Table 1, and the temperature was 260 to 300 ° C. using a twin-screw extruder (PCM30, manufactured by Ikegai Co., Ltd.).
To obtain a pellet. For each of the obtained pellets, a film having a thickness of 100 μm was prepared using a T-die film forming machine. Each of the obtained films was subjected to a tensile test. Further, using a plywood having a thickness of 10 mm as a base material, the above films were laminated with a urethane-based adhesive. The obtained laminate was evaluated for scratch resistance and cigarette resistance. Comparative Example 3 used the above synthetic mica, and Comparative Examples 4 and 5 used talc (“Micron White 5000SA” manufactured by Hayashi Kasei Co., Ltd.). Table 2 shows the above results.
Shown in

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

The decorative board of the present invention has high mechanical properties and thermal properties, and in particular, has excellent scratch resistance and cigarette resistance. Is useful in a wide range of fields such as vehicle interiors.

Continued on the front page F-term (reference) 2B002 AA01 AA02 AA03 BA01 BB06 DA02 DA04 DA06 4F100 AA33A AA33H AB01B AC03A AC03H AC05A AC05H AE09A AE09H AG00B AH00A AH00H AH03A AH03H AK01B02A02 AP02 DEA GB32 GB81 JB10A JB10H JB16A YY00A YY00H

Claims (7)

[Claims] 1. A decorative board comprising a resin composite obtained by uniformly dispersing a silicate composite comprising a swellable layered silicate and a positively charged organic compound in a thermoplastic resin. 2. The decorative board according to claim 1, wherein the resin composite contains 0.5 to 40 parts by weight of the silicate composite per 100 parts by weight of the thermoplastic resin. 3. The decorative board according to claim 1, wherein the thermoplastic resin is a polyamide resin. 4. The decorative board according to claim 1, wherein the swellable phyllosilicate is smectite or mica. 5. The decorative board according to claim 1, wherein the positively charged organic compound is a triazine-based compound. 6. A laminate for a decorative board comprising the decorative board according to any one of claims 1 to 5 and a substrate. 7. The laminate according to claim 6, wherein the base material is at least one selected from the group consisting of paper, wood board, plywood, synthetic resin, metal and glass.